1,3-Dipolar Cycloaddition Reactions of Low-Valent Rhodium and Iridium Complexes with Arylnitrile N-Oxides

  1. Ugur, I. 23
  2. Agopcan Cinar, S. 2
  3. Dedeoglu, B. 4
  4. Aviyente, V. 2
  5. Hawthorne, M.F. 5
  6. Liu, P. 3
  7. Liu, F. 3
  8. Houk, K.N. 3
  9. Jiménez-Osés, G. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Boğaziçi University
    info

    Boğaziçi University

    Estambul, Turquía

    ROR https://ror.org/03z9tma90

  3. 3 University of California Los Angeles
    info

    University of California Los Angeles

    Los Ángeles, Estados Unidos

    ROR https://ror.org/046rm7j60

  4. 4 Sabancı University
    info

    Sabancı University

    Estambul, Turquía

    ROR https://ror.org/049asqa32

  5. 5 University of Missouri
    info

    University of Missouri

    Columbia, Estados Unidos

    ROR https://ror.org/02ymw8z06

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Revista:
Journal of Organic Chemistry

ISSN: 0022-3263

Año de publicación: 2017

Volumen: 82

Número: 10

Páginas: 5096-5101

Tipo: Artículo

DOI: 10.1021/ACS.JOC.7B00282 SCOPUS: 2-s2.0-85019348691 WoS: WOS:000402023200008 GOOGLE SCHOLAR

Otras publicaciones en: Journal of Organic Chemistry

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Resumen

The reactions between low-valent Rh(I) and Ir(I) metal-carbonyl complexes and arylnitrile oxides possess the electronic and structural features of 1,3-dipolar cycloadditions. Density functional theory (DFT) calculations on these reactions, involving both cyclopentadienyl and carboranyl ligands on the metal carbonyl, explain the ease of the chemical processes and the stabilities of the resulting metallaisoxazolin-5-ones. The metal-carbonyl bond has partial double bond character according to the Wiberg index calculated through NBO analysis, and so the reaction can be considered a normal 1,3-dipolar cycloaddition involving M=C bonds. The rates of formation of the metallacycloadducts are controlled by distortion energy, analogous to their organic counterparts. The superior ability of anionic Ir complexes to share their electron density and accommodate higher oxidation states explains their calculated higher reactivity toward cycloaddition, as compared to Rh analogues. © 2017 American Chemical Society.